Sulfurized mono-esters of tall oil fatty acids and primary oxo alcohols

ABSTRACT

Sulfurized mono-esters of tall oil fatty acids and branched chain primary alcohols of six to 20 carbon atoms.

Carlson et a1.

1 1 SULFURIZED MONO-ESTERS OF TALL OIL FATTY, ACIDS AND PRIMARY 0X0 ALCOHOLS Inventors: Norman Arthur Carlson,

Wilmington; Bruce Hollis Garth, Newark, both of Del.

E. I. du Pont de Nemours and Company, Wilmington, Del.

Filed: Feb. 23, 1972 Appl. No.: 228,749

Assignee:

References Cited UNITED STATES PATENTS 2,179,065 11/1939 Smith 260/399 [111 I 3,817,971 1451 June 18, 1974 Smith 260/399 Primary ExaminerDonald E. Czaja Assistant Examiner-Eugene C. Rzucidlov Attorney, Agent, or Firm-Nicholas J. Masington, Jr.;

James A. Costello ABSTRACT Sulfurized mono-esters of tall oil fatty acids and branched chain primary alcohols of six to 20 carbon atoms 5 Claims, No Drawings SULFURIZED MONO-PETERS OF TALL OE FATTY ACIDS AND PRIMARY X0 ALCOHOIS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to sulfurized mono-esters. More particularly this invention relates to sulfurized tall oil fatty acid esters of C to C branched chain saturated primary alcohols, which esters are effective extreme pressure additives.

2. Description of the Prior Art Modern lubricants are complex mixtures of base lubricant fluids and additives. A lubricant additive is generally defined as a material which imparts a new and desirable property which is not possessed by the base lubricant fluid or which enhances certain desirable characteristics of such fluid. Additives are used for such purposes as to decrease oxidative and thermal degradation of the oil, reduce formation of deposits, reduce rust and corrosion, reduce friction and wear and to prevent destructive metal-to-metal contacts.

With the advent of high performance automobiles, the importance'and need for lubricant additives which prevent destructive metal-to-metal contact has greatly increased. As is well-known in the art, plain mineral oils provide good lubrication between moving metal parts as long as a film of oil is maintained between them. However, when pressures or rubbing speed between the moving metal surfaces are such that the film of oil is squeezed or wiped out, destructive metal-tometal contact occurs over a significant portion of the contacting metal surfaces. Adverse consequences of such metal-to-metal contact. often referred to as boundary lubrication, include welding, scoring, scuffing and in some cases. deformation or destruction of the lubricated components. Situations wherein boundary lubrication might occur include operating hypoid gears. automatic transmissions, limited slip differentials, metal cutting and metal drawing operations and the like. Extreme pressure (EP) additives are employed in the lubricants to prevent the above-described destructive metal-to-metal contact. It is believed that E? additives function by reacting with metal surfaces under boundary lubricating conditions to form an adherent film of metal salts. This film then acts as a solid lubricant when conditions of metal-to-metal contact occur. A necessary property of effective EP additives is that the formation of the film of metal salts takes place only at elevated temperatures which develop lo cally between the moving metal parts under conditions of boundary lubrication. If the formation of the metal salt film takes place under conditions other than that described above. for example at lower temperatures, excessive corrosion of the metal parts can take place whereas if the additive is too stable to react with the metal surface under boundary lubrication conditions, the additive will be ineffective as an extreme pressure additive.

The majority of art-known, effective EP additives are organic compounds which contain chemically bound sulfur, phosphorous, or chlorine or which contain functional groups such as carboxyl. Because of the lower cost, availability, and effectiveness, sulfurized sperm oil has been used extensively as an EP additive. Spenn oil is obtained from the head cavity and blubber of sperm whales, refined and sulfurized.

The well-known sulfurized sperm oil is principally sulfurized fatty acid mono-esters of relatively high molecular weight monohydric alcohols. Typically, the fatty acids are present in these whale oils as monoesters of high molecular weight alcohols. The alcohol portions of the whale oil monoesters are principally monohydric alcohols which are of corresponding chain length as the fatty acids and with about the same degree of unsaturation.

Sulfurized sperm oil of commerce is produced by treating refined sperm oil with sulfur in the temperature range of 300 to 385F. Crude sperm oil contains varying amounts of spermaceti and other solid waxes. In refining the crude sperm oils, these waxes are removed by refrigeration and pressing. In U.S. Pat. No. 2,179,066 a process of sulfurizing sperm oil is disclosed wherein the sperm oil is reacted with suitable amounts of sulfur at temperatures of about 300 to 385F., the reaction being continued until sulfur is combined in the fonn of neutral sulfur compounds.

Recently, however, there has been increasing concern over the rapid decrease in the world's whale population, and consequently importation of whale oil into the United States has been banned. It has thus become necessary to provide a substitute for sulfurized sperm oil.

It is known in the art to sulfurize mono-esters generally to produce sulfurized esters useful as lubricant additives. For example, Smith in U.S. Pat. No. 2,l79,065 discloses sulfurized esters prepared by sulfurizing compounds of the formula wherein R and R are straight chain aliphatic groups and at least one of R and R, being olefinic group.

Beretvas in U.S. Pat. No. 2,644,810 discloses a process for sulfurizing esters by treating mono-esters with sulfur chloride in the presence of water. The disclosed mono-esters suitable for sulfurization are unsaturated mono-esters of aliphatic acids having the general formula wherein R is a hydrocarbon group of straight chain aliphatic group or an unsaturated cycloaliphatic group, R is a straight chain aliphatic hydrocarbon group and X is oxygen or sulfur.

Generally, however, commercially available products suggested as replacements for sulfurized sperm oil have been deficient in at least one or more of the properties necessary for a useful EP additive, e. g. lack of solubility in base lubricant oil, lack of stability of solutions in base oil, insufficiently high flash point or in undesirably high pour point.

Sulfurized esters have now been discovered which are useful as extreme pressure additives, are inexpensive to produce; and have superior characteristics of good and stable solubility in lubricant bases, lower viscosities, higher flash points, and lower pour points. Those and the other objectives of the invention will be apparent from the discussion which follows.

SUMMARY OF THE INVENTION This invention is directed to a composition comprising sulfurized tall oil fatty acid esters of C to C branched chain saturated primary alcohols.

DESCRIPTION OF THE INVENTION It has now been discovered that when mono-esters of tall oil fatty acids and branched chain saturated primary alcohols of six to 20 carbon atoms are sulfurized, products suitable as lubricant additives are obtained. The sulfurized products are effective as extreme pressure additives and as anti-wear additives.-

Tall oil fatty acids useful in preparing the sulfurized mono-esters of the present invention are obtained from the spent black liquor of pulping processes. The black liquor is concentrated until the sodium salts of the various acids separate out and are skimmed off. The acids are obtained by acidification and then purified. Since tall oil fatty acids are by-products of extensive pulping operations, such acids are readily and economically available. Typically tall oil fatty acids contain mixtures of fatty acids having from about l4 carbon atoms to about 22 carbon atoms with oleic acid (50 percent) and linoleic acid (-42 percent) comprising the major portion of such acid mixtures. Tall oil fatty acids also contain small amounts of saturated acid, e.g., about I- l 0 percent as well as tract amounts of tri-unsaturated acids. Tall oil fatty acids comprising from about 75 to about 99% of unsaturated monocarboxylic acids having from l6 to l8 carbon atoms are particularly useful in the preparation of the sulfurized esters of the invention, a mixture of oleic and linoleic acids being most useful. Preferred tall oil fatty acids will comprise from about percent to about 50 percent by weight of oleic acid and from about 35 to about 50 percent of linoleic acid based on the total weight of the tall oil fatty acid. More preferred tall oil fatty acids comprise from about to about percent by weight of oleic acid and from about 50 to about 45 percent by weight of linoleic acid. While a single component of tall oil fatty acid e.g., all oleic acid may be used to prepare the sulfurized ester, the tall oil fatty acid containing the aforementinned mixture of acids is preferred since sulfurized esters prepared therefrom provide better (lower) pour point, and are available more economically.

The alcohols useful in preparing the products of the invention are branched chain saturated primary alcohols of six to 20 carbon atoms. Because of their availability and low cost, the preferred branched chain saturated aliphatic primary alcohols are oxo alcohols having from about six to about 20 carbon atoms. The oxo alcohols are produced by the art known process of subjecting an olefin. containing one less carbon than the desired alcohol. to a carbonylation reaction at pressures of from about L000 to 3,000 psi. and a temperature of from about 300 to 400F. with carbon monoxide and hydrogen in the presence of carbonylation catalyst such as cobalt carbonyl. The aldehydes which are the reaction products of this carbonylation reaction are then hydrogenated to form the desired alcohols.

Oxo hexyl alcohol, for example, is prepared by carbonylation and hydrogenation of an olefin which is prepared by the condensation of propylene and ethylene. The oxo hexyl alcohols contain 3 methyland 4 methylpentanols as principal branched chain saturated primary alcohols. The oxo alcohol of 8 carbon atoms is prepared by carbonylation and hydrogenation of propylene-butylene condensation product. The C oxo alcohols thus obtained are primary alcohols with dimethylhexanols being the major components thereof. Similarly, C oxo alcohols may be prepared from propylene trimer, C oxo alcohol from propylene tetramer, C oxo alcohols from propylene pentamers. In general,

' olefins containing one less carbon atom than the dc sired alcohol can be prepared by the proper combination of readily available olefins, for example, combining 5 parts of propylene with l part of butylene to form olefins containing 19 carbon atoms which can then be carbonylated and hydrogenated to provide oxo alcohol of 20 carbon atoms. While any one of the alcohols present in the oxo alcohols of six to 20 carbon atoms may be used alone to provide mono-ester of tall oil fatty acids which are then sulfurized, it is preferable to use oxo alcohols which are mixtures because of their availability and lower costs. The preferred oxo alcohol for the preparation of the products of the invention is oxo decyl alcohol.

The mono-esters of useful tall oil fatty acids and branched chain primary alcohols of six to 20 carbon atoms may be prepared by any art known esterification procedure. Esterification catalysts such as hydrochloric acid, sulfuric acid. ethanesulfonic acid, toluenesulfonic acid may be used. When the esterification process is carried out in steel vessels, mono-alkyl and dialkyl esters of ortho phosphoric acid may be used advantageously since the corrosion of steel vessels is minimized by their use.

The C C oxo alcohol mono-esters of tall oil fatty acids can be sulfurized by art-known methods. For example, a mixture of the mono-ester and sulfur can be heated to about C. to I80C. for about 7 hours. The sulfur may be any relatively good grade of sulfur such as flowers of sulfur or screened sulfur. Preferably the sulfur is in a subdivided state for ease of reaction and for better reaction control. The amount of sulfur used and the temperature employed will depend upon the particular sulfurized ester desired and con be readily determined by one skilled in the art.

Generally in the trade, sulfurized products are used as extreme pressure additives in three fields of applications: (1) Mild or low activity as in worm gear oils, manual gear box oils, motor oils, steam turbine oils, hydraulic oils and the like; (2) moderate" or intermediate as in hypoid gear oils and industrial gear oils; and (3) "high" activity as in cutting oils, metal drawing compounds. metal forming oils and in some hypoid gear oils. For mild or moderate activity, the sulfurized compounds usually contain about 10 percent or less of combined sulfur whereas for high activity the combined sulfur content is greater than about 10 percent, usually around 15-16%.

For the preparation of sulfurized esters of this invention of C to C oxo alcohols and tall oil fatty acids containing about 10 percent combined sulfur, heating of a mixture of the mono-ester with a slight excess (10 percent) of sulfur at about C. for about 7 to 12 hours will produce sulfurized ester containing about 10 percent combined sulfur, During the reaction a very small amount of hydrogen sulfide is evolved.

The sulfurized compositions of this invention normally contain from about 5 percent by weight to about 16 percent by weight of sulfur based on the weight of the sulfurized composition. For the preparation of sul- 1 of the lubricant composition, it is clear that sulfurized furized esters of this invention containing more than combined sulfur, the reaction is preferably carried out at around 160C. since at 180C. greater amounts of dehydrogenation reaction with accompanying great formation of hydrogen sulfide takes place.

As has been stated previously and will be shown in more detail in the examples, the compositions of this invention, i.e., the sulfurized C -C oxo alcohol monoesters of tall oil fatty acids, are effective extreme pressure additives for lubricants. The compositions of the invention have additional desirable properties such as bility. The sulfurized compositions of this invention are soluble to at least 50 percent by weight in solvent neutral oils and the resultant solutions are stable for extended periods of time.

For ease and safety in blending with lubricant base, it is often desirable that the sulfurized additives have low viscosity, high flash point and low pour point. A preferred composition of this invention, i.e., the oxo decyl ester of tall oil fatty acids sulfurized to contain about 10 percent combined sulfur has a viscosity of 61 SUS 'at 2l0F., flash point of 465F. and a pour point of -40F. By way of comparison, a typical sulfurized sperm oil containing about 10 percent combined sulfur has a viscosity of about 200 to 250 SUS at 210F., a

flash point of about 425F. and a pour point of to The compositions of this invention may be poured or pumped much more readily than sulfurized sperm oil for blending purposes because of the lower viscosity. and considerably lower pour point. Since the sulfurized ester may comprise up to about 20 percent by weight esters of low pour point are highly desirable, not only in that they facilitate formulation of the lubricant compositions. but also in that they do not increas e t he pour Acids (By gas chromatograph) Lower Boiling Acids, 7i

Palmitic Acid, 7r Palmitoleic Acid. Unknown Acid, Z

Stearic Acid, Olcic Acid Unknown Acid, 1 Linolcic Acid (cis-9,cisl 2)% Unknown Acid. 1 Unknown Acid, 7r

Linolcic Acid (cis-9. trans-l l Z Eicosanoic Acid.

Linolcic Acid (trans-9, trans-l l if Eicosadicnoic Acid, Eicosatricnoic Acid. Z Bchcnic Acid, Z Higher Boiling Acids, 16

point of the formulated lubricant. Further, it is clear to those skilled in theart that high pour point lubricants are not desirable. since they may provide inadequate lubrication at low temperatures.

In certain applications involving high speed and high torque services, lubricants containing lead soaps such as lead naphthenates in addition to the sulfurized'additives are often used. It is highly desirable therefore, that the sulfurized additives provide extreme pressure characteristics which can be utilized-in conjunction with the extreme pressure characteristics of the lead soaps. It is also highly important that the sulfurized additives be compatible (i.e., do not form precipitates) when mixed with lead soaps. The compositions of the present invention provide extreme pressure characteristics which complement the extreme pressure characteristics of lead naphthenate and the mixture of the sulfurized esters of this invention with lead naphthenate is compatible. As shown in Example 16, practicaly all of sulfurized products, now offered commercially as substitutes for sulfurized sperm oil are not compatible with lead naphthenate.

The lubricant base to which the compositions of the present invention may be added comprise any petroleum lubricating oil fraction such as a neutral or bright stock oil of any suitable viscosity. The amount of the sulfurized ester used and the particular viscosity of the lubricant base used will depend upon the particular use intended for the lubricant composition to be prepared. The sulfurized esters of the invention may be used together with the conventional lubricant additives such as antioxidants, anti-wear agents, viscosity index improvers, pour point depressants, and the like.

EXAMPLES The following examples are intended to be merely illustrative of the invention and not in limitation thereof. Unless otherwise indicated, all quantities are by weight.

EXAMPLE 1 This example describes the preparation of sulfurized tall oil fatty acid esters of oxy decyl alcohol. Tall oil fatty acids used were Acintol" Tall Oil Fatty Acids sold by Arizona Chemical Company. The Acintol tall oil fatty acids are available in several grades; the compositions and designations as supplied by the man ufacturer are given in the following table.

Table l TALL OIL FATTY ACIDS Tall Oil Fatty Acid Designation FA-l DGLR FA-l Special FA-Z FA-3 The oxo decyl alcohol was purchased from Enjay. I

ESTERI F lCATlON pletion of the esterification reaction (absence of absorbance due to carboxylic acid group). The reaction product mixture was then stripped for five hours by passing nitrogen into the charge at 180C. under a vacuum of about 20 to 50 mm. Hg pressure to remove unreacted alcohol. The yield of resultant Acintol" FA-3 oxo decyl ester was 7125 g. (theory 7128 g.).

SULFURlZATlON SULFUR) A mixture of 2816 g. of the Acintol FA-3 oxo decyl ester prepared above and 313 g. of screened sulfur was heated at 180C. under nitrogen sweep for 7 hours, then at 180C. and a vacuum of mm. Hg. pressure for 1 hour and finally at 180C. with nitrogen passage through the charge under a vacuum of 20 to 50 mm Hg. pressure for three hours. The exit gases were passed through a caustic scrubber containing 20 percent aqueous sodium hydroxide to trap a small amount of hydrogen sulfide evolved. The yield of sulfurized dark brown clear fluid was 3106 g. Analysis for sulfur showed combined sulfur content of 9.9 percent. The sulfurized ester had a viscosity of 61 SUS at 210F., a saponiflcation number of 145, an acid number of 2.1, flash point (Cleveland Open Cup) of 465F. and a pour point of 40F. The sulfurized ester exhibited excellent solubility in neutral solvent oils 100 SUS at 100F) of both naphthenic and paraffinic origins, being soluble to greater than 50 percent by weight at room room temperature. A 10 percent solution of the sulfurized ester in the above neutral oil stored over one month remained clear with no evidence of haze or precipitate.

Sulfurized esters containing less than about 12 percent combined sulfur can be prepared by essentially the general procedure described above, by using the appropriate amount of sulfur. Generally, the amount of sulfur used is about 10 percent in excess of the desired sulfur content of the final sulfurized product; however, anyone skilled in the art can readily determine the exact proportion of sulfur toester to be used to obtain the desired sulfur content in the sulfurized ester by relatively few experiments. When sulfurized esters containing more than about 12 percent sulfur are desired. it is preferable to carry out the sulfurization reaction at about 160C. instead of at 180C. in order to reduce the amount of dehydrogenation reaction.

EXAMPLES 2-14 Using the general procedures described in Example 1, additional sulfurized tall oil fatty esters were prepared. The useful additive property date of these esters including copper strip corrosion pour point, and solubility are set out in Table 11 below. Both the copper strip corrosion and the solubility tests were carried out with a 10 percent by volume solution of the sulfurized ester in 100 SUS/100F. solvent-refined neutral oil (Sun SSR-l 10, Sun Oil Co.). Copper strip corrosion tests were carried out according to ASTM D-130. 1n the ASTM D-l30 test, the results are indicated by classification by numbers of from 1 to 4 wherein 1 indicates very slight tarnish and 4 indicates extensive corrosion. The solubility test was carried out by keeping the 10 volume percent solution of the sulfurized ester in the neutral oil at room temperature and observing for the formation of haze or precipitate over a period of time. If the solution remained clear over a period of one month, the solubility is designated as satisfactory. The pour points of sulfurized esters were determined by ASTM D-97 method. The lowest temperature (F.) at which the sulfurized ester was observed to flow when cooled and examined under prescribed conditions is recorded as pour point.

These examples also illustrate that the compositions of the present invention show good copper strip corrosion resistance, good solubility characteristics and unexpectedly low pour point characteristics. As mentioned earlier, a typical sulfurized sperm oil has pour point in the range of 45 to F. The copper strip corrosion values of 4 as shown for examples 7, 8 and 9 are expected and desirable because sulfurized products containing greater than about 12 percent sulfur are generally used in applications requiring high extreme pressure activity, e.g., in cutting oils. Sulfur compounds having a high degree of activity are known in the industry as corrosive sulfur additives and thus require the degree of activity in corrosion tests indicated by the sempssfi w #5950 7, 8 and Table ll SULFURIZED TALL OIL FATTY ACID ESTERS Copper Pour Strip Solu- Combined Point c -i ion bility Example Acid Alcohol Sulfur I F. JI Ie t 2 Acintol" FA-3 Hexyl (cm) 10.2 15 l Satis 3 Acintol" FA-3 Decyl (0x0) 6.0 -20 1 do. 4 "Acintol" FA-3 Decyl (0x0) 9.3 40 1 do. 5 AcintoF FA-l Decyl (0x0) 9.8 .20 1 do. 6 Acintol" FA-3 Decyl (oxo) 12.0 20 1 do. 7 "Acintol" FA-3 Decyl (oxo) 13.6 20 4 do. 8 Acintol FA-3 Decyl (oxo) 15.7 40 4 do. 9 "Acintol" FA-3 Decyl (oxn) 16.0 20 4 do. 10 Olcic Decyl (oxo) 9.1 20 2 do. 1 l "Acintol" FA-3 n-Dccyl 9.9 +10 1 do. 12 Acintor' FA-3 Tridccyl (oxo) 9.7 40 1 do. 13 Acinto1" FA-3 n-Hcxadccyl 9.8 1 do. 14 Acintor' FA-3 Hexadecyl (0X0) 9.0 -45 1 do.

This example illustrates the extreme pressure additive activity of the sulfurized esters of this invention and in addition, compares the characteristics of the have good protection against scoring of metal surfaces in high speed and high torque services. This example shows that the sulfurized esters of this invention may be successfully used in conjunction with lead naphthenate n u s u s composltlons of this invention with some of the artand that y are eompatlble Wlth lead naphthenateknown products utilized in the trade as substitutes for Table IV shows the four ball weld point data of persulfurized sperm oil. The extreme pressure properties cent by volume of (a) the sulfurized ester of the Examwere determined y Fed ral T st Method tandard ple, (b) a 10 percent solution of lead naphthenate and The testeenslsts pressinga rotating 1 (c) of the combination of the sulfurized ester with lead sieel agamst a gl of speclmen'lubncated naphthenate. It is seen from the Table IV that the extlonary Steel balls- The test apparatus used w a treme pressure activity of the sulfurized esters of Exam- Four Ball Extreme Pressure Testercafrymg P the ple l compliments the extreme pressure activity of lead test 2 apphzd to z weldmg naphthenate when used together. The Four Ball Exi 5. mg Spi y a if il fi treme Pressure tests were carried out as described in e Ymg t o e Example using solvent neutral oil 100 SUS/l00F.) four balls. All tests were carrled out wlth 10 percent by as the base Oil volume of sulfurized products in 100 SUS/ 100F. neutral oil. The solubility tests, copper strip corrosion tests and pour point determination were carried out as de- I Table IV scrlbed n the prevlous examples. Flash polnt (Cleveland Open Cup) determinations were carried out ac- E A E COMBINATION cording to ASTM 0-92. The art-known commercially SULFUR'ZED ESTER LEAD NAPHT" N T Fm" Ba available products used in this example for comparison Weld Point(Kg.) with the products of the invention are designated A, B and C and since these products are offered with differ- Example 1 l I f f h d A 2 (b) l07r Lead Naphthenate 224 ent eve s o su ur, urt er eslgn atlons as (c) loq Example P'us etc. is used. The chemical composltlons of these com- 10% Lead Naphthenatc 400 mercially available sulfurized products were not determined. However, it is known that these products have been offered as commercial substitutes for sulfurized sperm oil. Also, for purposes of comparison the dat The date of Table V show that the sulfurlzed esters for a typical sulfurized sperm oil are also included. The of the Present ehe compatible lead p om arati e d m are t t i T bl III b l w, thenates. The compatlblllty test was carried out by add- Table III clearly shows that the sulfurized esters of ing lead naphthenate (3 percent) and various sulfurized the present invention possess extreme pressure lubriproducts (4percent) to a base lubricant stockprepared eating properties superior to the commercial products by mixing one part of 350 SUS/ 100F. neutral oil and B and C and in additiohhave highly deslrable charthree parts of bright stock. The mixtures were stored at fleiellstles of g flash Points low P P It 150F. and is inspected daily for deposit formation. lf should also be noted that the sulfurized esters of thls n- 40 no deposit f ti took place during the fi t' k ventlon haye higher flash point and lower pour po the composition was considered to pass the compatibilsulfur'zed sperm ity test. If the tested composition failed the test, the

A 7 I e number of days to failure is indicated in Table V. Com- Examp e 16 positions B1 and 2, Cl and 2 and D0 represent com- Lead soaps, such as lead naphthenate, are often used mercially available sulfurized products offered as sulfuwith sulfurized products to provide lubricants which rized sperm oil substitutes.

a wow... .ou lybl "TM COMPARISON OF SULFURlZED PRODUCTS Pour Flash Copper Weld Solubility Test Point Point Strip Test Composition Sulfur Initial 2 Weeks 1 Month Corrosion Kg. Load A-l 10-! l Satisfactory ppt. 410 l A-Z l4l5 Haze ppt. 4M) 4 B-l l0 Satisfactory Satisfactory Satisfactory 40 410 l 158 B-2 1 L5 do do. ppt. 40 4) l 178 8-3 l7 do. do Satisfactory 45 405 4 224 C4 10 do. do. ppt. 420 I l [2o (-2 l2 do. ppt. 141 Sulfurizcd I Sperm Oil l 1.5 do. Satisfactory Satisfactory 55 425 l 200 lmention Composition 7 of Example l 9.9 do. do. do. 40 465 l I78 Invention Composition of Example [6.0 do. do. do. 20 465 g 4 224 y' clear 'ppt- Table V LEAD NAPHTHENATE COMPATIBILITY Compatibility Test Composition %S Pass or Fail No.

- Days Sulfurized Sperm Oil l X Invention Composition of 9.9 X

Example 1 Commercial Product 8-] l0 X Commercial Product B-2 1 L5 X 1 Commercial Product C-l X 1 Commercial Product C-2 12 X 1 Commercial Product D l l X 5 Commercial Product E l0 X 5 Commercial Product F l0 X 5 Commercial Product G l l X l l. A composition comprising sulfurized tall oil fatty acid mono-esters of C to C branched chain saturated primary 0x0 alcohols wherein the amount of sulfur present is from about 5 to 16 percent based on total weight of the composition.

2. A composition according to claim 1 wherein the tall oil fatty acid of the ester comprises from about to about 99 percent by weight of unsaturated monocarboxylic acids having from 16 to 18 carbon atoms based on the total weight of the fatty acid.

3. A composition according to claim 1 wherein the tall oil fatty acid of the ester comprises from about 40 to about 50 percent by weight of oleic acid and from about 35 percent to about 50 percent by weight of linoleic acid based on the total weight of the fatty acid.

4. A composition according to claim 3 wherein the tall oil fatty acid of the ester comprises from about 45 to about 50 percent by weight of oleic acid and from about 40 percent to about 45 percent by weight of linoleic acid based on the total weight of the fatty acid.

5. A composition according to claim 1 wherein the oxo alcohol is oxo decyl alcohol. 

2. A composition according to claim 1 wherein the tall oil fatty acid of the ester comprises from about 75 to about 99 percent by weight of unsaturated monocarboxylic acids having from 16 to 18 carbon atoms based on the total weight of the fatty acid.
 3. A composition according to claim 1 wherein the tall oil fatty acid of the ester comprises from about 40 to about 50 percent by weight of oleic acid and from about 35 percent to about 50 percent by weight of linoleic acid based on the total weight of the fatty acid.
 4. A composition according to claim 3 wherein the tall oil fatty acid of the ester comprises from about 45 to about 50 percent by weight of oleic acid and from about 40 percent to about 45 percent by weight of linoleic acid based on the total weight of the fatty acid.
 5. A composition according to claim 1 wherein the oxo alcohol is oxo decyl alcohol. 